US11912653B2 - Noble metal-transition metal complex catalyst supported on carbon-coated silica-alumina support, and preparation method therefor - Google Patents
Noble metal-transition metal complex catalyst supported on carbon-coated silica-alumina support, and preparation method therefor Download PDFInfo
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- US11912653B2 US11912653B2 US16/958,430 US201816958430A US11912653B2 US 11912653 B2 US11912653 B2 US 11912653B2 US 201816958430 A US201816958430 A US 201816958430A US 11912653 B2 US11912653 B2 US 11912653B2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 15
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims description 52
- 229910052593 corundum Inorganic materials 0.000 claims description 30
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 229910000510 noble metal Inorganic materials 0.000 claims description 18
- 150000003624 transition metals Chemical class 0.000 claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007833 carbon precursor Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- 239000011369 resultant mixture Substances 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 235000003704 aspartic acid Nutrition 0.000 claims description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 229930006000 Sucrose Natural products 0.000 description 14
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 14
- 239000005720 sucrose Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- GGCUUOGRTPMFQK-UHFFFAOYSA-N dimethyl cyclohexane-1,1-dicarboxylate Chemical compound COC(=O)C1(C(=O)OC)CCCCC1 GGCUUOGRTPMFQK-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920006308 Indorama Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- TTXWERZRUCSUED-UHFFFAOYSA-N [Ru].[Sn] Chemical compound [Ru].[Sn] TTXWERZRUCSUED-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 125000005597 hydrazone group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/27—Polyhydroxylic alcohols containing saturated rings
- C07C31/272—Monocyclic
- C07C31/276—Monocyclic with a six-membered ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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Definitions
- the present invention relates to a noble metal-transition metal complex catalyst supported on a carbon-coated silica-alumina carrier (support) and a preparation method therefor, and more particularly, to a noble metal-transition metal complex catalyst supported on a carbon-coated silica-alumina carrier and a preparation method therefor, the catalyst being capable of obtaining a fast reaction rate and catalyst stability, as compared to a conventional catalyst, when cyclohexane dimethanol (CHDM) production is carried out by a cyclohexane dicarboxylic acid (CHDA) hydrogenation reaction in an aqueous solution by using a carbon-coated supported catalyst.
- CHDM cyclohexane dimethanol
- CHDA cyclohexane dicarboxylic acid
- Cyclohexane dimethanol (CHDM, 1,4-cyclohexanedimethanol) is the basic raw material for the preparation of polyester or polyamide resins.
- CHDM is commercially prepared in Asia by SK NJC, which is a joint-venture firm established by SK Chemicals, Mitsubishi Corporation, and Shin Nippon Rika.
- Indorama [old name: Eastman] is dominating the entire markets all over the world. In the CHDM market, a demand for high value-added polyester resins is increasing and is expected to increase in the future. Thus, stable supply and demand is required.
- Indorama produces 100 KTA of CHDM and SK NJC produces 20 KTA of CHDM. It is known that SK NJC plans to increase the production to 60 KTA by 2018. It is known that one production line has recently been expanded in two existing production lines.
- salt is produced by ionizing PTA of Sumitomo Seika Chemicals Co., Ltd. with NaOH in an aqueous solution to increase PTA solubility and a hydrogenation reaction is performed.
- This synthesis method has an advantage that lowers a hydrogenation reaction temperature as PTA solubility increases at a low temperature (40° C. to 130° C.).
- a process of neutralizing with HCl to recover Na + ions is required.
- the residual Na + salt reacts, it affects PETG polymerization.
- a brine solution containing NaCl incurs excessive wastewater treatment costs.
- a second method is a preparation method used by Indorama and SK NJC.
- Dimethyl terephthalate (DMT) is prepared by esterifying PTA and CHDM is prepared through dimethyl cyclohexane dicarboxylate (DMCD). Since this process uses a Cu-based or Cr-based catalyst when preparing CHDM from DMCD, it is relatively inexpensive in terms of catalyst price. However, since this process is a three-step preparation process (PTA DMT ⁇ DMCD CHDM), it is disadvantageous in terms of process. In addition, since different solvents are used in two processes, a large amount of wastewater is generated and DMT, which is more expensive than PTA, is used as the raw material.
- a third method is a process of preparing CHDM from PTA through CHDA. Since ruthenium, which is a noble metal, is used as an active metal in a CHDA hydrogenation reaction, it is disadvantageous in terms of catalyst price. However, since the final product CHDM can be obtained through the two-step process (PTA CHDA CHDM), it is determined that this process is advantageous in terms of cost reduction if the product cost is reduced through a reduction in process steps and the competitiveness of process technology is secured.
- the two-step process of preparing a CHDA and a CHDM through a PTA has a higher difficulty in a two-step reaction, which is a conversion reaction for converting a di-carboxylic acid into alcohol by hydrodeoxygenation, than a one-step reaction for saturating an aromatic ring of a TPA.
- the two-step process acts as a huddle in a commercialization stage. Therefore, it is urgent to develop a high efficiency/long life catalyst suitable for a CHDA hydrogenation process, which is a two-step reaction.
- the present invention aims to solve the above-described problems of the related art and the technical problems requested from the past.
- An object of the present invention is to provide a noble metal-transition metal complex catalyst supported on a carbon-coated silica-alumina carrier, capable of maintaining high activity and catalytic reaction stability when diol is prepared from a dicarboxylic acid using the noble metal-transition metal complex catalyst supported on carbon-coated silica-alumina (SiO 2 —Al 2 O 3 ), and a preparation method therefor.
- the present invention provides a noble metal-transition metal complex catalyst supported on a carbon-coated carrier.
- the catalyst is a complex catalyst in which noble metal-transition metal is supported on a carbon-coated silica-alumina carrier.
- alumina Al 2 O 3
- silica SiO 2
- 1 part by weight to 20 parts by weight of the noble metal and the transition metal may be included based on 100 parts by weight of the carbon-coated silica-alumina carrier.
- the noble metal may include one or more selected from the group consisting of palladium (Pd), rhodium (Rh), ruthenium (Ru), and platinum (Pt).
- an amount of the noble metal may be in a range of 1 part by weight to 10 parts by weight based on 100 parts by weight of the carrier.
- the transition metal may include one or more selected from the group consisting of tin (Sn), iron (Fe), rhenium (Re), and gallium (Ga).
- an amount of the transition metal may be in a range of 1 part by weight to 10 parts by weight based on 100 parts by weight of the carrier.
- a noble metal precursor and a transition metal precursor may be supported on the carrier at the same molar ratio.
- the carbon may be coated on the surface of the silica-alumina through a carbonization process.
- the present invention provides a hydrogenation method for hydrogenating a dicarboxylic acid group using the catalyst and a cyclohexane dimethanol (CHDM) prepared by performing a hydrogenation reaction of a cyclohexane dicarboxylic acid (CHDA) on the catalyst.
- CHDM cyclohexane dimethanol
- the dicarboxylic acid may be one selected from the group consisting of an oxalic acid, a malonic acid, a succinic acid, a glutaric acid, an adipic acid, a pimelic acid, a suberic acid, an azelaic acid, a sebacic acid, a malic acid, an aspartic acid, a glutamic acid, a phthalic acid, an isopthalic acid, a terephthalic acid, and a cyclohexane dicarboxylic acid.
- the present invention provides a method for preparing a noble metal-transition metal complex catalyst supported on a carbon-coated silica-alumina carrier, the method including:
- the carbon precursor and the boric acid may be added at a weight ratio of 1:0.005 to 1:0.1.
- the complex in the step (a), may be prepared by being supported on the carrier by incipient-wetness impregnation.
- the carbonization process may be performed in a temperature range of 300° C. to 700° C. in a nitrogen atmosphere.
- the noble metal and the transition metal may be supported in 1 part by weight to 20 parts by weight based on 100 parts by weight of the carrier.
- the reduction process in the step (d), may be performed in a temperature range of 400° C. to 600° C.
- a noble metal-transition metal catalyst supported on a carbon-coated silica-alumina carrier and a preparation method therefor have an effect that can maintain high activity and catalytic reaction stability when diol is prepared from a dicarboxylic acid using a noble metal-transition metal catalyst supported on carbon-coated silica-alumina (SiO 2 —Al 2 O 3 ).
- FIG. 1 is a schematic diagram of a preparation process in which a noble metal-transition metal is supported on a carbon-coated silica-alumina carrier, according to an embodiment of the present invention.
- FIG. 2 is a graph showing the results of a CHDM production reaction using a catalyst in which a noble metal-transition metal is supported on a carbon-coated silica-alumina carrier, according to an embodiment of the present invention.
- FIG. 3 is a graph showing the results of a CHDM production reaction using a catalyst in which a noble metal-transition metal is supported on a carbon-uncoated silica-alumina carrier, according to an embodiment of the present invention.
- FIG. 4 is graphs showing CHDM production reaction efficiency results using a catalyst in which a noble metal-transition metal is supported on a carbon-coated silica-alumina carrier and a carbon-uncoated silica-alumina carrier, according to an embodiment of the present invention.
- substitution means that one or more hydrogen atoms in the functional groups of the present invention are substituted with one or more substituents selected from the group consisting of a halogen atom (—F, —Cl, —Br, or —I), a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, an ester group, a ketone group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a halogen atom (—F, —Cl, —Br, or —I),
- substituted means that a hydrogen atom is substituted with a substituent such as a halogen atom, a C 1 -C 20 hydrocarbon group, a C 1 -C 20 alkoxy group, and a C 6 -C 20 aryloxy group.
- hydrocarbon group refers to a linear, branched, or cyclic saturated or unsaturated hydrocarbon group.
- the alkyl group, the alkenyl group, the alkynyl group, and the like may be linear, branched, or cyclic.
- alkyl group refers to a C 1 -C 30 alkyl group and the term “aryl group” refers to a C 6 -C 30 aryl group.
- heterocyclic group refers to a group in which one to three heteroatoms selected from the group consisting of O, S, N, P, Si, and any combination thereof are contained in one ring. Examples of the heterocyclic group may include pyridine, thiophene, and pyrazine, but the present invention is not limited thereto.
- the term “dicarboxylic acid” refers to an organic acid having two carboxylic acid functional groups in one molecule.
- the molecular formula of the dicarboxylic acid is HOOC—R—COOH.
- R is preferably an alkyl group or an aryl group.
- the conventional cyclohexane dicarboxylic acid (CHDA) hydrogenation reaction technology has a limitation in the preparation of the cyclohexane dimethanol (CHDM) using a catalyst having a high reaction activity and hydrothermal stability, as compared to a conventional catalyst, while using an inexpensive carrier.
- the present invention solves the above problems by providing a noble metal-transition metal catalyst in which a noble metal-transition metal is supported on a carbon-coated silica-alumina carrier, wherein 40 parts by weight to 95 parts by weight of alumina (Al 2 O 3 ) and 5 parts by weight to 60 parts by weight of silica (SiO 2 ) are included based on 100 parts by weight of the carrier, and 1 part by weight to 20 parts by weight of the noble metal and the transition metal are included based on 100 parts by weight of the carbon-coated silica-alumina carrier.
- the carrier can act as a catalyst poison under the influence of acid
- metal oxides such as silica, alumina, zirconium oxide, and titanium dioxide
- complex oxides such as silica-alumina, acidic activated carbon, zeolite, and the like may be used.
- a structure of gamma alumina may be changed to a boehmite structure under hydrothermal reaction conditions. Therefore, as a method for increasing the hydrothermal stability of alumina, various methods of performing pretreatment with second other components have been introduced. Also, when silica is used as a carrier, since a bond between cobalt and the carrier is strong as compared to an alumina carrier, a decrease in the reducibility of the cobalt metal in a reduction process and thus a decrease in its activity are observed. As a method for overcoming this problem, a method of pre-treating a silica surface using a metal such as zirconium has been introduced as a conventional technique.
- the carrier of the present invention since two components of Al 2 O 3 and SiO 2 are present at the same time, the disadvantages when the alumina component and the silica component are used alone is improved.
- a solution including a carbon precursor is supported on the alumina-silica carrier through incipient-wetness impregnation to form a complex, and the complex is used as a catalyst for a dicarboxylic acid hydrogenation reaction through carbonization.
- an amount of the alumina component may be preferably in a range of 40 parts by weight to 95 parts by weight based on 100 parts by weight of the entire carrier.
- the amount of the alumina component may be in a range of preferably 55 parts by weight to 85 parts by weight, and more preferably 80 parts by weight to 85 parts by weight.
- a high acid point of the silica-alumina carrier may cause by-products to be excessively generated by hydrocracking during the reaction.
- the amount of the alumina component exceeds 95 parts by weight, a problem may occur in hydrothermal stability of alumina. Therefore, the above range is preferable.
- An amount of the silica component may be preferably in a range of 5 parts by weight to 60 parts by weight based on 100 parts by weight of the entire carrier.
- the amount of the silica component may be in a range of preferably 5 parts by weight to 35 parts by weight, and more preferably 5 parts by weight to 10 parts by weight.
- a problem may occur in hydrothermal stability of alumina.
- the amount of the silica component exceeds 50 parts by weight, a high acid point of the silica-alumina carrier may cause hydrocracking. Therefore, the above range is preferable.
- the noble metal may include one or more selected from the group consisting of palladium (Pd), rhodium (Rh), ruthenium (Ru), and platinum (Pt).
- an amount of the noble metal may be in a range of 1 part by weight to 20 parts by weight based on 100 parts by weight of the carbon-coated silica-alumina carrier.
- the amount of the noble metal may be in a range of preferably 1 part by weight to 10 parts by weight, and more preferably 3 parts by weight to 8 parts by weight. In this case, when the amount of the noble metal is less than 1 part by weight, the conversion efficiency is low and thus the production efficiency is reduced. When the amount of the noble metal exceeds 10 parts by weight, additional cost may be incurred in a process due to a high catalyst price and low selectivity of the target product. Therefore, the above range is preferable.
- the transition metal may include one or more selected from the group consisting of tin (Sn), iron (Fe), rhenium (Re), and gallium (Ga).
- an amount of the transition metal may be in a range of 1 part by weight to 20 parts by weight based on 100 parts by weight of the carbon-coated silica-alumina carrier.
- the amount of the transition metal may be in a range of preferably 1 part by weight to 10 parts by weight, and more preferably 3 parts by weight to 8 parts by weight. In this case, when the amount of the transition metal is less than 1 part by weight, the conversion efficiency of the reaction is lowered or the selectivity of the target product is lowered. Thus, excessive separation and recovery costs in the process may be used.
- the amount of the transition metal exceeds 10 parts by weight, additional processes may be required due to the occurrence of many by-products.
- the present invention provides a hydrogenation method using the above-described catalyst, and in a specific example, a cyclohexane dimethanol (CHDM) may be prepared through a cyclohexane dicarboxylic acid (CHDA) hydrogenation reaction on a catalyst.
- CHDM cyclohexane dimethanol
- CHDA cyclohexane dicarboxylic acid
- the present invention provides a method for preparing a noble metal-transition metal complex catalyst supported on a carbon-coated carrier.
- the method includes: preparing a complex by dissolving a boric acid in an aqueous carbon precursor solution and supporting the resultant mixture on silica-alumina (SiO 2 —Al 2 O 3 ); carbonizing the complex; supporting a noble metal-transition metal on a carbon-coated silica-alumina (SiO 2 —Al 2 O 3 ) carrier; and reducing a noble metal-transition metal oxide supported on the silica-alumina (SiO 2 —Al 2 O 3 ) carrier with hydrogen.
- a boric acid is dissolved in an aqueous carbon precursor solution and supported on a silica-alumina (SiO 2 —Al 2 O 3 ) to prepare a complex.
- a carbonization process is performed by introducing the complex at a temperature of 500° C. in a nitrogen atmosphere.
- the noble metal precursor and the transition metal precursor having the above-described content ratio are supported on the carbon-coated silica-alumina (SiO 2 —Al 2 O 3 ) carrier by co-impregnation, such that the noble metal-transition metal oxide is reduced with hydrogen.
- a catalyst including the noble metal-transition metal in the carbon-coated carrier is prepared.
- the carbon precursor and the boric acid added to the aqueous carbon precursor solution may be added at a weight ratio of 1:0.005 to 1:0.1.
- the carbon precursor and the boric acid may be added at a weight ratio of preferably 1:0.007 to 1:0.07, and more preferably 1:0.01 to 1:0.05.
- the weight ratio of the boric acid is less than 0.005
- the electronic charge density of the active metal decreases and the amount of hydrogen adsorption decreases, resulting in a decrease in the catalytic reaction activity.
- the weight ratio of the boric acid exceeds 0.1, an excessive amount of the boric acid is dissolved in the target product and a problem may occur in product quality. Therefore, the above range is preferable.
- sucrose sucrose
- boric acid Aldrich
- the carbonization was performed at 300° C. for 3 hours.
- the sucrose was attached to the surface of SiO 2 —Al 2 O 3 through dehydration between the hydroxyl group and the sucrose on the surface of SiO 2 —Al 2 O 3 .
- the sucrose attached to the surface was changed to a polycyclic aromatic carbon sheet after the carbonization process was performed at 500° C. for 3 hours.
- the carbonization process was performed under a condition that nitrogen flowed at 100 cc/min and a ramping rate was 5° C./min.
- ruthenium precursor RuCl 3 , Kojima
- a tin precursor SnCl 2 , Aldrich
- 5 parts by weight of ruthenium based on 100 parts by weight of the C—SiO 2 —Al 2 O 3 carrier was supported.
- the amount of the tin was supported in the same number of moles as ruthenium and reduced at 500° C. for 3 hours (100 cc/min H 2 :30/N 2 :70), and this was used as a catalyst for a dicarboxylic acid hydrogenation reaction.
- a ruthenium-tin catalyst (Ru—Sn/C—SiO 2 —Al 2 O 3 ) supported on C—SiO 2 —Al 2 O 3 was applied to a hydroconversion reaction of dicarboxylic acid into diol.
- a cyclohexanedicarboxylic acid (CHDA) represented by a dicarboxylic acid was selected and converted into cyclohexanedimethanol (CHDM) through selective hydrogenation. This reaction was performed in a liquid phase reaction, and an acid-resistant titania batch reactor was used.
- a high-temperature and high-pressure autoclave reactor was filled with a CHDA as a reactant and a catalyst at a weight ratio of 3.75:1 and was filled with distilled water as a reaction solvent.
- the amount of the reactant relative to the reaction solvent was fixed to 7 wt %.
- the reactor was pressurized to a reaction pressure by using hydrogen, such that whether the reactor leaked was checked through a hydrogen detector. Oxygen inside the reactor was completely removed by depressurization and purging. Finally, the pressure inside the reactor was set to 10 bar, the reactor was heated to the reaction temperature, and the reactor was pressurized to the reaction pressure of the hydrogen atmosphere. Then, the reaction was performed for 6 hours.
- the reaction was performed at 90° C. and 90 bar for 6 hours, and the stirring was maintained at a speed of 1,000 rpm by using an overhead impeller. After the reaction, the reactor was cooled to room temperature and decompressed, such that the catalyst and the liquid product were separated by filtration and analyzed by gas chromatography with an HP-1 column.
- the conversion rate, selectivity, and yield of a CHDM, a CHMA, ester, and the like generated according to the CHDA conversion were calculated using Equations 1 to 3:
- the long-term stability test was performed while the reaction for evaluating the performance of the Ru—Sn/C—SiO 2 —Al 2 O 3 catalyst in producing the CHDM through the CHDA hydrogenation reaction was performed a total of 10 times, and the results thereof are shown in FIG. 2 .
- the reaction was performed for 6 hours in the hydrogen atmosphere at 230° C. and 90 bar.
- a Ru—Sn/SiO 2 —Al 2 O 3 catalyst was prepared in the same manner as in Example 1, except for the process of coating carbon.
- a Ru—Sn/C—Al 2 O 3 catalyst was prepared by using an Al 2 O 3 carrier, instead of a SiO 2 —Al 2 O 3 carrier, so as to verify the performance and durability of the Ru—Sn/C—SiO 2 —Al 2 O 3 catalyst.
- a catalyst preparation method was performed in the same manner as in the method for preparing the C—SiO 2 —Al 2 O 3 carrier in Example 1, except that SiO 2 —Al 2 O 3 was changed to Al 2 O 3 .
- sucrose (Aldrich) was added to 10 ml of distilled water and stirred using a magnetic stirrer. After the sucrose was completely dissolved in the distilled water, 0.2 g of boric acid (Aldrich) was added and dissolved in an aqueous sucrose solution for 2 hours. Subsequently, the solution was supported on an Al 2 O 3 carrier through incipient-wetness impregnation.
- the carbonization was performed at 300° C. for 3 hours.
- the sucrose was attached to the surface of Al 2 O 3 through dehydration between the hydroxyl group and the sucrose on the surface of Al 2 O 3 .
- the sucrose attached to the surface was changed to a polycyclic aromatic carbon sheet after the carbonization process was performed at 300° C. for 3 hours.
- the carbonization process was performed under a condition that nitrogen flowed at 100 cc/min and a ramping rate was 5° C./min.
- ruthenium precursor RuCl 3 , Kojima
- a tin precursor SnCl 2 , Aldrich
- the catalyst supported ruthenium in 5 parts by weight based on 100 parts by weight of the C—Al 2 O 3 carrier.
- the amount of the tin was supported in the same number of moles as ruthenium and reduced at 500° C. for 3 hours (100 cc/min H 2 :30/N 2 :70), and this was used as a catalyst for a dicarboxylic acid hydrogenation reaction.
Abstract
Description
-
- (a) preparing a complex by dissolving a boric acid in an aqueous carbon precursor solution and supporting the resultant mixture on silica-alumina (SiO2—Al2O3);
- (b) carbonizing the complex;
- (c) supporting a noble metal-transition metal on a carbon-coated silica-alumina (SiO2—Al2O3) carrier; and
- (d) reducing a noble metal-transition metal oxide supported on the silica-alumina (SiO2—Al2O3) carrier with hydrogen.
Claims (12)
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